Tertiary arylation

Tertiary alkylamines illustrate no useful chemistry on nitrosation Tertiary aryl-amines undergo nitrosation of the ring by electrophilic aromatic substitution... 

Tertiary aryl phosphines react with 2,4-dinitrochlorobenzene to form the salts... 

The complexes ci -[PtCl(SnCl3)P2] may be obtained starting from either a cis-bis-phosphine complex of a tertiary aryl phosphine or a chelating diphosphine, e.g. PPh3 or DIOP complexes (20), (although careful examination of the P-31 spectra of the monodentate systems suggests that the trans isomer is also present). 

Reaction of the partially fluorinated aliphatic aromatic ketone 22 with bromotrifiuoromethane/ tris(diethylamino)phosphane leads to formation of the tertiary aryl alcohol 23. ° ... 

Functionalized tertiary aryl phosphines play an important role in transition metal coordination chemistry. These compounds have been used as ligands in synthesis, catalysis, mechanistic studies, and in the study of coordination compounds as structural models. In this contribution the syntheses of two new types of these ligands, tertiary aryl phosphines functionalized by an amide group, are detailed. The published coordination chemistry of these compounds includes the study of intramolecular N—H oxidative addition, the synthesis of chelates stabilized amido complexes, and the preparation of complexes with both ftve- and six-membered chelate rings. ... 

The crystalline solid has been stored in air for several months without any detectable decomposition. It displays the solubility properties expected for a tertiary aryl phosphine It is soluble in ethers, chloroform, toluene, and acetone, but insoluble in hexane and ethanol. IR(Nujol mull) = 3350cm ... 

Organolithium reagents (primary, secondary, tertiary, aryl and vinyl) also add in excellent yield to a-alkoxyaldehyde dimethylhydrazones (146) equation 19) with high threo diastereoselectivity (Table 9). Hydrogenolytic cleavage of the resultant hydrazines provide an attractive route to rAreo-2-amino alcohols. 

Reductive alkylation of anilines is a very convenient and broadfy used method to synthesize secondary and tertiary aryl amines. Many exan les were described both in the primary literature and in reviews, nickel, palladium or platinum catafysts being recommended without any strong preference [3]. Surprisingly, we could not find any information on the reductive alkylation of highly sterically hindered anilines like MEA. 

The product formed when the nitrogen of a tertiary amine shares its lone pair with a nitrosonium ion caimot be stabilized by loss of a proton. A tertiary aryl amine, therefore, can undergo an electrophilic aromatic substitution reaction with a nitrosonium ion. The product of the reaction is primarily the para isomer because the bulky dialkyl-amino group blocks approach of the nitrosonium ion to the ortho position. 

They also reported preparations of various cross-linkers containing tertiary aryl groups with polymerizable carbon-carbon double bonds [20]. 

To reach a decision on the mechanism for participation by nitrogen in (80a), Grob et al. prepared and solvolyzed the series of tertiary aryl-substituted p-nitrobenzoates (83) and (84) (Table 11). A plot of log k for... 

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